Atomically thin quasi-two-dimensional materials like graphene and transition metal dichalcogenide (TMDC) layers exhibit extraordinary optical and electrical properties. They have not only been used as testing grounds for fundamental research but also show promise for their viability in optoelectronics, photovoltaics and photocatalysis, to name a few technological applications. In practice, seldom are these materials used in isolation. One often finds them as part of a multicomponent structure, or heterostructure. In a similar spirit as the influence of solvents on the properties of molecular complexes, nanomaterials are also affected by their dielectric environment. Engineering the effect of the surroundings on the excitations in these materials is both a challenge and an opportunity. Moreover, understanding the transport of energy and charge through these heterostructures is crucial for device design. In this dissertation I will explore the properties of excitations in zero-dimensional and two-dimensional nanostructures and their dependence on the details of the environment using optical spectroscopy. Here, I discuss three of the projects that I undertook during my graduate studies. The first project concerns the efficient near-field, non-radiative energy transfer (NRET) of photo-excited carriers from semiconductor nanocrystals to graphene and a TMDC, molybdenum disulfide. Photoluminescence quenching of single quantum dots and time-resolved photoluminescence were used to quantify the rate of energy transfer. The NRET rate exhibited surprisingly opposite trends with increasing number of layers of the acceptor 2D sheet. The rate increased with increasing thickness of adjacent graphene layers but decreased with increasing thickness of MoS₂. A model based on classical electromagnetism could successfully explain the countervailing trends in terms of the competition between the dissipative channels and reduction of the electric field within the 2D material. In the next project, the exciton binding energy and band gap in another TMDC, monolayer WS₂, were tuned via dielectric screening from the environment. Monolayers of WS₂ were capped with graphene layers of varying thickness (1 – 4 layers). The excitonic states of WS₂ in the resulting heterostructures were detected using reflectance contrast spectroscopy and theoretically studied by a semi-classical model. The binding energy of the exciton was halved to 150 meV by placement of a single layer of graphene adjacent to the WS₂. Furthermore, this dramatic decrease in the binding energy is accompanied by a reduction of the band gap by the same amount. Additionally, the average spacing between the graphene and WS₂ was also identified to be a critical parameter with respect to dielectric screening of the electron - hole interaction. This offers a flexible alternative for the external manipulation of the Coulomb interaction. In the final part, I study how excitons in WS₂ couple and scatter with the excitations of the lattice or phonons. The importance of this study stems from the contribution of the scattering rates to the spectral width of the excitonic feature, the dephasing dynamics and thermal transport. The transition from direct to indirect band gap semiconductor from mono- to bilayer is expected to add an additional scattering channel via phonon emission. Through temperature dependent reflectance contrast and photoluminescence spectroscopy, the scattering rate for the phonon emission and absorption processes have been quantified. Comparing the results to data reported in the literature, it is understood that the striking change for the scattering rates is expected only at the mono- to bilayer transition for WS₂. The results suggest material thickness as a handle for engineering exciton - phonon interactions at the nanoscale.

When nature is observed at the nanoscale, quantum physics is typically the most accurate model to describe and predict its behavior. Furthermore, quantum effects are increasingly at the core of the operation of new advanced electronic and photonic devices, which, in some cases, are designed on the basis of controlling quantum systems. This thesis focuses on two such systems, united by the methods used to realize them. These methods represent the cutting-edge of nanofabrication, which is the structuring of matter at ultra-small dimensions with a degree of precision and control that has not been previously attained. Pushing these methods to their limits enables the emergence of unique phenomena in the quantum systems explored here. The first system involves the realization of artificial graphene in an AlGaAs/GaAs quantum heterostructure. The appearance of massless charge carriers in graphene, which are described by the relativistic Dirac equation, originates from the linear energy-momentum dispersion of the electronic states in proximity to the K and K’ points of the hexagonal Brillouin zone. This unique quantum behavior is a direct result of the honeycomb symmetry of the graphene lattice. The prospect of reproducing this physics in an adjustable, artificial honeycomb lattice, known as artificial graphene, offers a platform for the exploration of novel quantum regimes of massless Dirac fermions beyond the limits imposed by the inability to manipulate the lattice of the natural material. The electronic properties of a two-dimensional electron gas whose density is modulated by a periodic potential with honeycomb symmetry have been predicted to generate massless Dirac-fermions with tunable Fermi velocity. This thesis reports the observation of a graphene-like band structure in a modulation-doped AlGaAs/GaAs quantum well engineered with a honeycomb lateral surface superlattice. This was accomplished by reactive ion etching of the surface to within a few tens of nanometers from the quantum well. A metal hard-mask, patterned by electron beam lithography combined with metal deposition and lift-off, was used to form a honeycomb artificial lattice with a variable lattice period, down to 40 nm. This is a three-fold reduction with respect to the smallest reported to date in pertinent literature. The BCl3-based shallow etching produces cylindrical pillars below which the two-dimensional electron gas is expected to form quantum dots, where the electron density is higher than in the surrounding etched regions. Low-temperature resonant inelastic light scattering measurements reveal new electronic transitions. An accurate interpretation of these can be found in the joint density of states derived from the calculated graphene-like linearly-dispersed energy bands, induced by the honeycomb potential modulation. The second system comprises the nanoscale engineering of individual electron spin qubits in diamond. Spin systems in solid-state have been intensively investigated as an outstanding pathway towards quantum information processing. One of the advantages of solid-state spintronics is the possibility of applying nanofabrication techniques commonly used by the semiconductor industry to produce and integrate spin qubits. The negatively charged nitrogen-vacancy (NV-) center in diamond stands out because of its optically addressable spin, which shows long coherence time and viable spin initiation, manipulation and read-out. A central challenge has been the positioning of NV- centers with nanometer scale control, that would allow for efficient and consistent dipolar coupling and the integration within an optoelectronic device. I demonstrate a method for chip-scale fabrication of arrays of closely-spaced NV- centers with record spatial localization of approximately 10 nm in all three dimensions and controllable inter-NV spacing as small as 40 nm. This is the highest spatial resolution realized to date in positioning NV- centers at the nanoscale with high throughput, and approaches the length scale of strong dipolar coupling. This method used masked implantation of nitrogen in an ultra-pure CVD-grown diamond substrate through nano-apertures in a thin gold film, patterned via electron-beam lithography and dry etching. The high-density and high-atomic weight of gold results in a mask which is significantly thinner than polymer films used in other works, whilst still successfully impeding ion penetration, with a mask contrast of more than 40 dB. This process allows for the creation of apertures with lower aspect ratio which are therefore easier to pattern in close proximity to one another, i.e., within the dipolar coupling range. The position and spin coherence properties of the resulting near-surface NVs were measured through wide-field super-resolution optically detected magnetic resonance imaging, Hahn echo and CPMG pulsed microwave spectroscopy. The patterning methodology demonstrated here is optimally suited to functional integration with plasmonic nanostructures, which can enhance our ability to control single-photon emission with the prospect of creating near-surface nanoscale sensors of electric or magnetic fields and quantum optoelectronic devices.

Utilizando a técnica de epitaxia por feixe molecular (MBE), crescemos heteroestruturas tensionadas de InxGa1-xAs sobre substratos de GaAs (100). A composição de In, a espessura para a transição 2D-3D e a espessura crítica (hc) foram determinadas através da análise \"in situ\" pelo RHEED. Os valores da hc e da espessura para a transição 2D- 3D foram observadas ser funções da composição do In e da temperatura do substrato. Um estudo do efeito da desorientação do substrato de GaAs (100) de alguns graus sobre as qualidades ópticas (PL) de poços quânticos simples e múltiplos de InxGa1-xAs/GaAs também foi realizado. Microscopia eletrônica por transmissão (TEM) foi utilizada para a verificação da qualidade das interfaces dos poços quânticos de InxGa1-x/GaAs. Algumas estruturas de dupla barreira (AlGaAs/GaAs/InAs/GaAs/AlGaAs) foram crescidas e caracterizadas opticamente (PL) / InxGa1-xAs strained heterostructures were grown on GaAs (100) by Molecular Beam Epitaxy (MBE). Indium concentration (x), 2D-3D growth mode transition thickness and critical thickness (hc) were determined by \"in situ\" RHEED analysis. Hc and 2D-3D growth mode transition thickness values were verified to depend on In concentration and substrate temperature. The dependence of the InxGa1-xAs /GaAs simple and multiple quantum wells (SQW and MQW) PL optical quality on the GaAs (100) substrate misorientation was also studied. The SQW interfaces were investigated by Transmission Eletronic Microscopy (TEM). Some double-barrier structures (AlGaAs/GaAs/InAs/GaAs/AlGaAs was also grown and optically characterized

Esta tese trata da modelagem das características eletrônicas de dispositivos semicondutores baseados em contatos Schottky heterodimensionais, definidos como contatos entre um metal e um sistema de dimensionalidade reduzida. Especificamente, este trabalho concentra-se na situação em que o metal é posto em contato direto com um gás eletrônico bidimensional presente na interface de uma heterojunção empregando dopagem modulada. Dispositivos de interesse são diodos Schottky, bem como estruturas do tipo metal-semicondutor-metal (MSM). Para a característica capacitância-tensão, C-V, é desenvolvido um modelo quasi-bidimensional que apresenta excelente concordância com os resultados experimentais disponíveis. Do ponto de vista da característica corrente-tensão, I-V, é apresentado um modelo unificado, considerando tanto o mecanismo de tunelamento, quanto o de emissão termoiônica. Nossas previsões teóricas, suportadas por alguns indicativos experimentais, sugerem que, para aplicações em fotodetecção, o uso de contatos heterodimensionais, substituindo junções metal-semicondutor convencionais, pode reduzir a corrente de escuro em pelo menos uma ordem de magnitude. / This thesis deals with the modeling of the electronic characteristics of semiconductor devices based on heterodimensional Schottky contacts, defined as contacts between a metal and a reduced dimensionality system. Specifically, this work focus on the situation in which a metal is placed in direct contact with a two dimensional electron gas located at the interface of a modulation doped heterojunction. Devices of interest are Schottky diodes as well as metal-semiconductor-metal (MSM) structures. For the capacitance-voltage characteristics a quasi two-dimensional model is developed, which yields very good agreement with available experimental results. For the current-voltage characteristics a unified model is presented, considering the tunneling as well as the thermionic emission mechanisms. Our theoretical predictions, supported by a few experimental findings, suggest that, for photodetection applications, the use of heterodimensional contacts, replacing conventional metal-semiconductor junctions, can reduce the dark current by at least one order of magnitude.

The production of large area, high quality two-dimensional (2D) materials using chemical vapour deposition (CVD) has been an important and difficult topic in contemporary materials science research, after the discovery of the diverse and extraordinary properties exhibited by these materials. This thesis mainly focuses on the CVD synthesis of two 2D materials; bilayer graphene and monolayer tungsten disulphide (WS2). Various factors influencing the growth of each material were studied in order to understand how they affect the quality, uniformity, and size of the 2D films produced. Following this, these materials were combined to fabricate 2D vertical heterostructures, which were then spectroscopically examined and characterised. By conducting ambient pressure CVD growth with a flat support, it was found that high uniform bilayer graphene could be grown on the centimetre scale. The flat support provides for the consistent delivery of precursor to the copper catalyst for graphene growth. These results provide important insights not only into the upscaling of CVD methods for growing large area, high quality graphene and but also in how to transfer the product onto flexible substrates for potential applications as a transparent conducting electrode. Monolayer WS2 is of interest for use in optoelectronic devices due to its direct bandgap and high photoluminescence (PL) intensity. This thesis shows how the controlled addition of hydrogen into the CVD growth of WS2 can lead to separately distributed domains or centimetre scale continuous monolayer films at ambient pressure without the need for seed molecules, specially prepared substrates or low pressure vacuum systems. This CVD reaction is simple and efficient, ideal for mass-production of large area monolayer WS2. Subsequent studies showed that hexagonal domains of monolayer WS2 can have discrete segmentation in their PL emission intensity, forming symmetric patterns with alternating bright and dark regions. Analysis of the PL spectra shows differences in the exciton to trion ratio, indicating variations in the exciton recombination dynamics. These results provide important insights into the spatially varying properties of these CVD-grown TMDs materials, which may be important for their effective implementation in fast photo sensors and optical switches. Finally, by introducing a novel non-aqueous transfer method, it was possible to create vertical stacks of mixed 2D layers containing a strained monolayer of WS2, boron nitride, and graphene. Stronger interactions between WS2 on graphene was found when swapping water for IPA, likely resulting from reduced contamination between the layers associated with aqueous impurities. This transfer method is suitable for layer by layer control of 2D material vertical stacks and is shown to be possible for all CVD grown samples, a result which opens up pathways for the rapid large scale fabrication of vertical heterostructure systems with large area coverage and controllable thickness on the atomic level.

Made available in DSpace on 2015-04-22T22:07:25Z (GMT). No. of bitstreams: 1 DISSERTACAO-JOSE DILSON.pdf: 2263133 bytes, checksum: bbf5adbba042abf3bd96506b874e8845 (MD5) Previous issue date: 2009-04-02 / Fundação de Amparo à Pesquisa do Estado do Amazonas / The scattering matrix technique is used to calculate the transmissivity of polarized spins through semiconductors heterostructures of asymmetrical double barrier. The movement of electrons is described in the effective mass approach of the Dresselhaus-Rashba.models.The transmissivity and polarization are calculated as a function of electron energy with kk = 0.5 × 106 cm−1, kk = 1 × 106 cm−1, kk = 1.5 × 106 cm−1 e kk = 2 × 106 cm−1 varying the angle φ InAs/GaSb/InAs/GaSb/InAs system. Fixing the parallel moment kk and varying φ = 0◦, 15◦, 30◦, 60◦, 75◦, and 90◦ we observed that the positions of the resonant picks vary faintly with the energy and the transmission curves change more strongly in the areas out of the resonance with the polarization reaching values among 10% − 82% in the resonant levels.For the directions φ = 45◦ and 135◦ the spin mixing produces an efficiency of polarization of 100% and the effects of the Dresselhaus and Rashba spin-orbit interactions are shown quite favorable to the engineered for fabricating of spin filters and spintronics devices. / A técnica da matriz de espalhamento é usada para calcular a transmissividade de spins polarizados, através de heteroestruturas semicondutoras de dupla barreira assimétrica. O movimento de elétrons de condução são descritos na aproximação da massa efetiva dos modelos de Dresselhaus-Rashba. A transmissividade e a polarização são calculadas como função da energia do elétron para kk = 0, 5×106 cm−1, kk = 1×106 cm−1, kk = 1, 5×106 cm−1 e kk = 2×106 cm−1, com vários valores de φ, para um sistema InAs/GaSb/InAs/GaSb/InAs. Fixando o momento paralelo kk e variando φ = 0◦, 15◦, 30◦, 60◦, 75◦, e 90◦ observamos que as posições dos picos ressonantes variam fracamente com a energia e as curvas de transmissão mudam mais fortemente nas regiões fora da ressonância com a polarização atingindo valores entre 10% −→ 82% nos níveis ressonantes. Para as direções φ = 45◦ e 135◦ o spin mixing produz uma eficiência de polarização de 100% e os efeitos das interações spin-órbita de Dresselhaus e Rashba mostram-se bastante favoráveis à engenharia na fabricação de filtrode spin e dispositivos spintrônicos.

Made available in DSpace on 2015-04-22T22:07:29Z (GMT). No. of bitstreams: 1 SALOME_ FONTAO_CUNHA.pdf: 1002004 bytes, checksum: d7451d75aca7e8b7ef22bdbdd99db48c (MD5) Previous issue date: 2005-07-29 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Estudamos o transporte de buracos em dupla barreira ressonante submetida a stress uniaxial, usando a técnica da matriz de espalhamento na aproximação de massa efetiva do modelo de Luttinger-Kohn-Pikus. A transmissividade é calculada para k = 0 e k ≠ 0 para o sistema GaAs /AlAs para os esforços de compressão (T < 0) e tração (T > 0). Para k = 0, os buracos leves e pesados são desacoplados e observa-se um deslocamento rígido nas curvas de transmissividades e inversão do estado fundamental, HH1 LH1 para o esforço de tração. No caso k ≠ 0, além da mistura das bandas que aumenta a probabilidade de transmissão, o stress muda o caráter das partícula HH LH, a separação relativa entre os estados HH e LH no poço quântico, e indiretamente, influência na mistura dos estados de valência, aumentando ou diminuindo as transmissividades dos buracos dependendo do tipo de esforço aplicado.

Este estudo propôs uma avaliação do papel dos três principais parâmetros clássicos da síntese do nitreto de carbono grafítico: temperatura final, tempo de permanência na temperatura final e taxa de aquecimento. Realizou-se a otimização da síntese, via metodologia de superfície de resposta, usando-se como variável-resposta a degradação fotocatalítica de um poluente-modelo (tartrazina). A significância estatística dos fatores foi confirmada, com 95% de confiança. Em seguida, um modelo de segunda ordem foi ajustado às melhores respostas e, no ponto de máxima degradação, as condições foram: 605oC por 183 min, com taxa de aquecimento de 5oC min-1. A taxa de degradação com o fotocatalisador sintetizado foi aproximadamente três vezes maior que a da fotólise. As amostras da região de melhores respostas foram analisadas em uma série de experimentos de caracterização, sendo eles: difratometria de raios X, espectroscopia na região do infravermelho médio, área superficial específica, microscopias de varredura (MEV e MEV-FEG), potencial zeta e espectroscopia de reflectância difusa na região do ultravioleta-visível. O fotocatalisador com maior atividade apresentou menor energia de band gap e maior área superficial especifica do que as relatadas na literatura (2,59 eV e 29,5 m2 g-1, respectivamente). Foram criadas heteroestruturas entre o fotocatalisador sintetizado e o trióxido de tungstênio. A partir de uma série de caracterizações básicas, confirmou-se a formação da heteroestrutura. Com essa heteroestrutura, a taxa de degradação foi aproximadamente cinco vezes maior que a com o nitreto de carbono grafítico. / This study proposed an assessment of the role of the three major classical parameters for synthesizing graphitic carbon nitride: final temperature, residence time at the final temperature and heating rate. The synthesis was optimized, via response surface methodology, using the photocatalytic degradation of a model pollutant (tatrazine) as the response-variable. The statistical significance of the factors was confirmed, within 95% confidence level. Afterwards, a second-order model was adjusted to the better responses and, at the maximum degradation point, the conditions were: 605oC for 183 min, with heating rate of 5oC min-1. The degradation rate with the synthetized photocatalyst was approximately three times greater than the photolytic one. The samples from the better response region were analyzed in a series of characterization experiments: X ray diffractometry, mid-infrared spectrometry, specific surface area, scanning electron microscopy (SEM and FEG-SEM), zeta potential, and ultraviolet-visible diffuse reflectance spectroscopy. The most active photocatalyst showed smaller band gap energy and greater specific surface area than the ones reported in literature (2.59 eV and 29.5 m2 g-1, respectively). Heterostructures were formed between the synthetized photocatalyst and tungsten trioxide. A series of basic characterization techniques confirmed the heterostructure formation. Using this heterostructure, the degradation rate was approximately five times greater than the one with graphitic carbon nitride.

This thesis studies the physics of multilayer heterostructures grown from topological insulators (TIs), primarily bismuth selenide and antimony telluride, and other topologically trivial materials. This is done by extending a standard low-energy 3D TI Hamiltonian and varying its associated material parameters across the simulation domain. New results arising from the position-dependent TI interface model are found. For the first time, this method is incorporated into a density-functional theory (DFT) solver in order to study the self-consistent charge density in multilayer TI heterostructures due to the interface states. The thesis is structured as follows. The introduction (Ch. 1) presents a pedagogical review of the theory of 3D TIs and low-energy Hamiltonians used to study them, as well as typical methods in solid state physics that are made use of throughout the thesis. Chapter 2 presents the position-dependent Hamiltonian, showing new evidence for topological features of bulk states including varying degrees of band mixing and inversion; also, interface state tunnelling is shown to be affected by atomic layer orbital overlap, and incomplete localisation of surface states is demonstrated for antimony telluride. Chapter 3 presents a new DFT model of TI heterostructure interfaces and shows how conduction through TI interface states can be controlled with an electric field. Chapter 4 covers the extension of the model in Ch. 1 to 2D cross-sections of TI wires and heterostructures, showing for the first time evidence of localisation of conduction almost entirely within the inner interfaces of a 2D heterostructure wire. Chapter 5 presents our work with magnetic fields, demonstrating evolution of interface and bulk states with changing magnetic field and Landau level, as well as presenting new evidence for more complex spin structures in bismuth selenide arising from Landé factor signs. Our conclusions are presented in Chapter 6.

Neste trabalho desenvolvemos rotinas computacionais em Python para o cálculo de propriedades dinâmicas (espectros de fotocorrente e absorção) de heteroestruturas semicondutoras baseadas em Dinâmica Quântica. Em uma primeira etapa do desenvolvimento do projeto, a formulação baseada na evolução temporal das soluções da equação de Schrödinger dependente do tempo foi aplicada a sistemas com soluções analíticas conhecidas ou com resultados já reportados na literatura. Devido à excelente concordância entre nossos dados e aqueles já conhecidos, em uma etapa seguinte, foram calculadas as energias de transição observadas em espectros de fotoluminescência para poços quânticos de InGaAs/GaAs, crescidos por MBE, levando-se em conta os efeitos de tensão e segregação de átomos de índio. Na continuidade do projeto, especial atenção foi dada ao desenvolvimento de estratégias para calcular os espectros de absorção e fotocorrente para dispositivos do Estado Sólido. O conjunto de resultados apresentados neste trabalho demonstra que a metodologia desenvolvida é precisa e pode ser utilizada com baixo custo computacional para o modelamento de heteroestruturas semicondutoras mais complexas, que servem de base para o desenvolvimento de dispositivos optoeletrônicos. / In this work we developed computational routines in Python for the calculation of the dynamic properties (spectrum of photocurrent and absorption) of semiconductor heterostructures based on Quantum Dynamics Theory. In a first stage of the development of the project the formulation based on the time evolution of the solutions of the time dependent Schrödinger equation was applied to systems with known analytical solutions or results already reported in the literature. Due to the excellent agreement between our data and those already known, in the next stage the transition energies observed in photoluminescence spectra for InGaAs/GaAs quantum wells, grown by MBE, were calculated taking into account the effects of stress and segregation of indium atoms. In the continuity of the project, special attention was given to the development of strategies to calculate absorption and photocurrent spectra for solid state devices. The set of results presented in this work demonstrates that the methodology developed is accurate and can be used with low computational cost for the modeling of more complex semiconductor heterostructures, which are used for the development of optoelectronic devices.